Method of coating three dimensional objects with molecular sieves

ABSTRACT

A method of coating a substrate with an oriented film. A target is ablated to create a plume. The substrate is manipulated, which may be by vibration, in the plume to coat the substrate with a film. The film is heated in a synthesis gel of the target to form the oriented film.

[0001] The government may own rights in the present invention pursuantto grant number 009741-055, UTD Account No. 2-23206, from Texas HigherEducation Coordinating Board-Advanced Technology Program.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to a method of coating threedimensional and non-uniform objects with molecular sieves using pulsedlaser deposition.

[0004] 2. Description of Related Art

[0005] There are a variety of methods for fabricating molecular sievesinto thin films. A popular approach is the seed method, which involvesthe deposition of colloidal suspensions of zeolite nanosols onto a flatsubstrate followed by a controlled secondary growth of thenanoparticles. The resulting films are generally continuous andsometimes oriented. It appears, however, that the seed method works bestwith only a few types of zeolites, especially those with crystalmorphologies that efficiently pack on the substrate surface such aszeolite NaA or ZSM-5. This also implies that this method works best onflat surfaces. Consequently, there are relatively few examples ofzeolite films and no examples of oriented films on non-planar surfaces.

[0006] The deposition-during-synthesis technique has been used to growzeolite Beta onto macroporous alumina spheres with a 4% loading byimmersing the support in the synthesis mixture. Analogously, metal andceramic monoliths have also been coated with zeolite Beta, Mordenite,and ZSM-5 utilizing this technique. Molecular sieve films prepared bythe direct deposition of crystals from solution, however, often sufferfrom defects and poor adhesion. Furthermore, controlling the filmthickness and orientation can be quite a challenge.

SUMMARY OF THE INVENTION

[0007] In one respect, the invention is a method of coating a substrate.A target is provided. Material is ablated from the target to create aplume. The substrate is manipulated in the plume to coat the substratewith a film, and the film is heated in a synthesis gel of the target. Inanother respect, the invention is a coated substrate made by thismethod.

[0008] In other aspects, the heating of the film forms an oriented film.The oriented film may include crystals normal to the surface of thesubstrate. The target may include a zeolite. The zeolite may include atleast one of UTD-1, ZSM-5, Beta, Mordenite , NaX, NaA, SSZ-33, SSZ-31,SSZ-42, MCM-22, or a mixture thereof. The target may include aphosphate. The phosphate may include an aluminum phosphate. The aluminumphosphate may include at least one of VPI-5, AlPO₄-5, AlPO₄-8, or amixture thereof. The phosphate may include a silicon aluminum phosphate.The silicon aluminum phosphate may include at least one of SAPO-5,SAPO-37, SAPO-42, or a mixture thereof. The phosphate may include ametal aluminum phosphate. The metal aluminum phosphate may include atleast one of MAPO-39, MAPO-5, MAPO-11, UCSB-6, UCSB7, or a mixturethereof. The target may include a mesoporous molecular sieve. Themesoporous molecular sieve may include at least one of MCM-41, MCM-48,SBA-15, SBA-16, Nb-TMS-1, Ti-TMS-1, Ta-TMS-1, or a mixture thereof Theablating may include subjecting the target to pulsed radiation from anexcimer laser. The laser may include a KrF* laser operating betweenabout 70 and about 200 mJ/pulse with a repetition rate between about 1and about 50 Hz. The manipulating may include moving the plume relativeto the substrate. The manipulating may include vibrating the substrate.The heating may include heating between about 1 hour and about 200hours. The method may also include adjusting a background pressure ofthe substrate to between about 150 mTorr and about 350 mTorr. Thebackground pressure may include a background pressure of O₂. Thesubstrate may include a zeolite crystal, glass, metal, metal oxide, orplastic. The substrate may include a porous substrate. The largestdimension of the substrate may be between about 10 nm and about 10 mm.The substrate may be spherical. The method may also include washing orcalcining the oriented film.

[0009] In another respect, the invention is a method of coating asubstrate with an oriented film. A target including Cp*₂Co⁺ or Cp₂Fe isprovided. Material is laser ablated from the target to create a plume.The substrate is vibrated in the plume to coat a film on the substrate,and the film is heated in a synthesis gel of the target to form theoriented film. In another respect, the invention is a coated substratemade by this method.

[0010] In other aspects, the laser ablating may include a first stageand a second stage. The first stage ablates material at a first laserpower and the second stage ablates material at a second laser power, thefirst laser power being different than the second laser power.

[0011] In another respect, the invention is a method of coating asubstrate with an oriented film. A target including Cp*₂Co⁺ or Cp₂Fe isprovided. Pulsed laser radiation having an energy between about 70mJ/pulse and about 200 mJ/pulse at a repetition rate of between about 1Hz and about 50 Hz is directed to the target to create a plume. Thesubstrate is heated. A pressure between about 150 mTorr and about 350mTorr about the substrate is maintained. The substrate is vibratedwithin the plume to coat a film on the substrate, and the film is heatedin a synthesis gel of the target to form the oriented film. In anotherrespect, the invention is a coated substrate made by this method.

[0012] In other aspects, the method may also include washing orcalcining the oriented film.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following drawings form part of the present specification andare included to further demonstrate certain aspects of the presentinvention. The invention may be better understood by reference to one ormore of these drawings in combination with the detailed description ofspecific embodiments presented herein.

[0014]FIG. 1A. Schematic diagram of 3-D objects manipulated in a laserablation plume by vibration.

[0015]FIG. 1B. Side view schematic of an apparatus for vibrating objectsin a laser ablation plume.

[0016]FIG. 1C. Top view schematic of an apparatus for vibrating objectsin a laser ablation plume.

[0017]FIG. 2. Scanning electron micrograph of pulsed-laser deposited(PLD) glass bead after a multi-staged deposition time of 35 min.

[0018]FIG. 3A. Scanning electron micrograph of post hydrothermallytreated PLD glass beads after a multi-staged deposition time of 35 min.

[0019]FIG. 3B. Higher magnification scanning electron micrograph of posthydrothermally treated PLD glass beads after a multi-staged depositiontime of 35 min.

[0020]FIG. 4. Cross section of post hydrothermally treated PLD glassbeads after a multi-staged deposition time of 35 min.

[0021]FIG. 5. Higher magnification scanning electron micrograph ofhydrothermally treated PLD glass beads after sonicating for one hour indeionized water.

[0022]FIG. 6. Scanning electron micrograph of hydrothermally treated PLDglass beads after calcining in air at about 550° C. for about 6 hours.

[0023]FIG. 7. Cross-section of PLD UTD-1 film covering a metal beadfabricated with about a 13 minute deposition time and about a 70mJ/pulse laser power.

[0024]FIG. 8A. Scanning electron micrograph of a post hydrothermallytreated PLD metal bead.

[0025]FIG. 8B. Higher magnification scanning electron micrograph of apost hydrothermally treated PLD metal bead.

[0026]FIG. 9. Cross section of a post hydrothermally treated PLD metalbead.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0027] Laser ablation offers a distinct advantage of being able to coatnon-planar surfaces by manipulating an object in a laser ablation plumeor by manipulating the direction of the plume. Using the disclosedmethods, the utility of pulsed laser deposition (PLD) may be extended toinclude microscale objects such as catalyst particles and catalystsupports. In order to evenly coat three-dimensional objects by PLD, onemay move the objects in the ablation plume or may likewise move theplume relative to the object. Mechanical manipulation may not always befeasible on small length scales. However, a method of vibrating anobject in a laser ablation plume sufficiently manipulates an object toensure that it is coated in three-dimensions.

[0028] In one disclosed embodiment, a pancake vibrator may providesufficient motion for small substrates, such as metal or glass beads, inan ablation plume to be evenly coated with zeolites, phosphates,mesoporous materials, or other materials. For example, the presentlydisclosed methods may be used to coat three dimensional objects with amolecular sieve coating. A three dimensional substrate may be placed inor on a vibrating apparatus and may be subjected to a plume generated bylaser ablation of a target. The vibrating medium may rotate andgenerally, manipulate, the substrate, exposing, over time, its entiretyto the plume to form a laser-deposited film covering the substrate. Thesubstrate may then be hydrothermally treated to form an orientedcoating.

[0029] In one embodiment, post hydrothermal treatment includes heatingPLD coated substrates in a synthesis gel of the material used as atarget during ablation. Thus, in embodiments utilizing a UTD-1 target,post hydrothermal treatment may include heating UTD-1 PLD substrates ina UTD-1 synthesis gel, while for MAPO-39 coatings a MAPO-39 synthesisgel may be used. Heating times, temperatures, and conditions may bevaried to achieve an oriented film. In a particular UTD-1 embodiment,however, heating may be at about 175° C. for about 72 hours.

[0030] In one embodiment, crystals may be oriented so thatone-dimensional channels may be normal to the substrate. A detaileddiscussion of methods used to form oriented films using laser ablationmay be found in co-pending U.S. patent application Ser. No. ______ filedMay 21, 1999 and entitled, “Preparation Of Laser Deposited OrientedFilms And Membranes” by Kenneth J. Balkus, Jr., Mary E. Kinsel, and LisaL. Washmon, which is incorporated herein by reference in its entirety.

[0031] In one embodiment, small (about 75 μm) beads may be coated withan oriented film via laser ablation. The coating may be with UTD-1molecular sieves, but it will be understood with the benefit of thepresent disclosure that a variety of other materials including, but notlimited to, zeolites such as ZSM-5, Beta, Mordenite , NaX, NaA, SSZ-33,SSZ-31, SSZ-42, MCM-22, aluminum phosphates such as VPI-5, AlPO₄-5,AlPO₄-8; silicon aluminum phosphates such as SAPO-5, SAPO-37, SAPO-42;metal aluminum phosphates such as MAPO-39, MAPO-5, MAPO-11, UCSB-6,UCSB-7; mesoporous molecular sieves such as MCM-41, MCM-48, SBA-15,SBA-16, Nb-TMS-1, Ti-TMS-1, and Ta-TMS-1 may be used as a coating aswell. Thus, although description herein may be directed to, for example,UTD-1 coatings for convenience, those having skill in the art willunderstand that description herein applies to many other coatingmaterials as well including, but not limited to, the coatings listedabove. Targets used in methods described herein may include anultraviolet absorbing material including, but not limited, to, theorganometallic cobalticinium ion CP*₂Co⁺ or the related ferrocene Cp₂Feto facilitate ablation. It will be understood that other UV absorbingmaterials suitable for aiding in ablation may be substituted therewith.

[0032] Substrates may be various materials and may include, but are notlimited to, zeolite crystals, glass, metal, metal oxide, or plastics.Substrates may be of various configurations including, but not limitedto, flat substrates or substrates having a nonplanar topology.Substrates may be of any shape and/or size suitable for applying acoating by the methods described herein. In one embodiment, substratesmay include fibers, such as optical fibers.

[0033] In one embodiment, about 0.025 g (which may be equivalent toabout 100 small spherical beads) may be loaded into a substrate holder,configured to vibrate, without any pretreatment. The vibrating substrateholder allows the beads to move and rotate freely in a UTD-1 laserablation plume. In this embodiment, the laser ablation of anassynthesized UTD-1 target for about 5 minutes at a power of about 159mJ/pulse results in coated beads as shown in FIG. 2.

[0034] When high laser power of about 100 to about 150 mJ/pulse is used,the laser beam may tend to eject some large fragments of the UTD-1target material onto the surface of the substrate. Thus, a lower laserpower from about 50 to about 80 mJ/pulse may be used to achieve lesstarget splashing on the surface.

[0035] Other embodiments achieving an ablated film that is continuousand thick enough to provide a protective covering for a glass substratemay involve increasing deposition time from between about 5 to about 25minutes, followed by an additional 10 minutes to provide a PLD film ofgreater than about 1.75 μm.

[0036] In such an embodiment, the first coating may be done utilizinglow laser power (about 69 mJ/pulse) that provides a tight, denselypacked uniform film with less splashing of the target material. A secondcoating may be applied utilizing a higher laser power (about 138mJ/pulse) for about 10 minutes during which some splashing may occur. Inthis embodiment, the glass beads may be completely coated with a thickPLD film.

[0037]FIG. 2 shows an SEM image of a multi-staged PLD glass bead thatwas coated for about 25 minutes at low laser power, and for about 10minutes at high laser power. This image shows no evidence of anydiscontinuity on the surface of the substrate. The larger fragments fromsplashing may be seen dispersed around the entire glass bead surface. Itappears that the large fragments from splashing are sitting on top ofthe thin layer of the laser deposited zeolite film.

[0038] A post hydrothermal treatment may be applied to the thicklycoated film as described herein. FIG. 3A shows an SEM image of a glassbead after post hydrothermal treatment, and it may be noted that theoriginal size of the glass bead here was not diminished. In fact, thediameter of the glass bead increased from about 75 μm to about 90 μm.Random crystal aggregates obtained from a synthesis gel used in the posthydrothermal treatment may be seen in the background of the image. UTD-1crystals appear to be attached to the glass beads radiating up from theglass bead surface.

[0039]FIG. 3B shows an SEM image taken at a higher magnification of thehydrothermally treated glass bead. The UTD-1 crystals may be seenradiating up from the laser deposited surface with plank-likemorphology. The crystals appear to be normal to the surface of thespheres, creating a preferred orientation of the UTD-1 crystals in whichthe one-dimensional channels run in parallel along the length of theplanks. Loosely attached random crystals may also be seen on the surfaceof the oriented crystals. X-ray diffraction analysis confirms the phaseidentity of UTD-1.

[0040] A cross section of the UTD-1 PLD film may be taken in order toobtain a film thickness of a post hydrothermally treated PLD film. FIG.4 shows an SEM image in which UTD-1 crystals may be seen radiating upfrom the surface of the glass bead. The crystals also appeared to bedensely packed, which is consistent with the theory that as thefragments reorganize they are forced to grow substantially vertically.The film appears to be in the range of about 7 to about 9 microns thick.This is consistent with the increase in diameter of the glass beadsubstrate shown in FIG. 3A.

[0041] The preferred orientation of the reorganized film is alsocomparable to thick films (about 11 μm) that have been formed on flatsubstrates after pulsed laser deposition (PLD). However, crystals onflat substrates have appeared to be more densely packed at the surfacedue to the planar morphology of the substrate. Additionally, thecrystals from the glass beads appeared to be smaller than the crystalsgenerated from the flat substrates, while being larger than the crystalsgenerated in the bulk gel synthesis.

[0042] It appeared that the crystals may be strongly adhered to thesurface of the substrate since there was no loss of film upon handling.Glass substrates used herein were too small to under go a scratch testto confirm film adhesion. Retention of the film after sonication may,however, be supporting evidence for the strong adhesion of the film tothe substrate. Therefore, glass beads may be subjected to a one-hoursonication in deionized water to test the adhesion of the films.

[0043] FIGS. 5 shows an SEM image of glass beads after such sonication.In FIG. 5, the UTD-1 hydrothermally treated film appeared to still beattached to the glass beads after sonication. FIGS. 5 illustrates aconsequence of a static hydrothermal treatment. Some of the glass beadsin the figures appeared to have oriented themselves in a close-packingarrangement, and it appeared that they were held together by inter-growncrystals. Also, FIG. 5 shows the effect of the beads resting in thebottom of the reactor, where flat spots may be seen. In light of this, are-growth step may benefit from a stirred or rotated system so the beadsmay remain dispersed in the post hydrothermal treatment. This imagereveals the UTD-1 crystal radiating themselves around the glass beads.The sonication test supported the proposition that the hydrothermallytreated films were well adhered to glass substrates.

[0044] Thermal stability of films prepared in accordance with thepresent disclosure may be tested by calcining glass beads in air atabout 550° C. for about 5 hours. After calcination, the film may changefrom a yellow color to a gray color upon decomposition ofbis(pentamethylcyclopentadienly)cobalt (III) ion Cp*₂Co⁺ template in thepost hydrothermal treatment gel. The SEM image of FIG. 6 revealed thatan oriented UTD-1 film may still remain on a glass bead even afterthermal stress. In FIG. 9, there were some randomly oriented crystals onthe surface of the oriented crystals that were probably deposited fromthe bulk gel.

[0045] The above data provided evidence that post hydrothermally grownfilms on 3-D objects may become well adhered to a substrate and thatthey may be thermally stable up to temperatures of at least about 550°C.

[0046] In one embodiment, PLD films may be grown on three-dimensionalmetal substrates. Metal spheres, including steel spheres, may be used assubstrates. In one embodiment, spherical, zinc galvanized coated steelbuck shot pellets measuring about 0.5 mm in diameter may be used assubstrates. In one embodiment, untreated metal beads (such as six toeight untreated metal beads) may be loaded into a vibrating substrateholder. Heating the substrates in an oxygen atmosphere may promoteadhesion to the interface where the energetic particles form covalentbonds with the metal surface. An oxide linkage at the surface/filminterface may account for strong adhesion of the film as shown by theretention of the film to the metal bead after an etching test with adiamond scribe.

[0047] In one embodiment, the metal sphere is a fairly smooth non-planarsubstrate with some imperfections across the surface. It is possiblethat such scattered defects that are present on the surface may promotefilm adhesion by providing crevices for the crystals to nucleate. In oneexample, after pulsed laser deposition of UTD-1 for about 10 minutes ata laser power of about 123 mJ/pulse, a film may be achieved.

[0048] Splashing may result in larger fragments on the surface. TheUTD-1 fragments from splashing, some as large as a micron, may be evenlydispersed around the surface of the bead. In order to obtain lesssplashing, a laser power of about 70 mJ/pulse may be used. With theexception of a lower laser power, the deposition parameters may beanalogous to the conditions required for flat pulsed laser depositedUTD-1 films as disclosed for example, in co-pending U.S. patentapplication Ser. No. ______ filed May 21, 1999 and entitled,“Preparation Of Laser Deposited Oriented Films And Membranes” by KennethJ. Balkus, Jr., Mary E. Kinsel, and Lisa L. Washmon. By decreasing thelaser power, however, a uniform well-adhered thin deposited film may beachieved on the substrate where the PLD fragments were small, tightlypacked, and uniform throughout the entire surface of the bead.

[0049]FIG. 7 shows a cross section of the PLD film. The film wasestimated to be about 900 nm thick, which corresponds to a depositionrate of about 70 nm/min. This film was thin compared to the PLD filmrequired for glass beads because the metal beads may better withstandhigh pH conditions present in the hydrothermal treatment gel. Thereappeared to be no exposed areas on the surface of the substrate afterPLD. The film was still well-adhered to the substrate even after etchingthe surface with the diamond scribe. A loosely bound film most likelywould have flaked off the surface when subjected to such a test.

[0050] PLD films from a UTD-1 target were mostly amorphous to x-rays,which is consistent with results obtained with glass beads. In oneembodiment, the PLD UTD-1 film coating metal substrates may behydrothermally treated as previously described by placing the metalballs in a Teflon lined Parr reactor containing the UTD-1 synthesis gelmixture for, in one embodiment, about 72 hours at about 175° C. understatic conditions.

[0051]FIG. 8A and FIG. 8B show SEM images at different magnifications ofresulting post hydrothermally treated metal spheres. FIG. 8A shows whatappeared to be a new, thick layer surrounding the metal sphere that wasnot present before hydrothermal treatment. The post hydrothermallytreated film was continuous, and covered the entire surface of the beadwith no observable voids on the surface. A closer inspection of thethick layer revealed highly crystalline film that was confirmed as UTD-1by powder x-ray diffraction (XRD).

[0052]FIG. 8B shows the UTD-1 crystals having a plank-like morphologyradiating up from the substrate surface. The crystals appeared to benormal to the surface of the spheres, creating a preferred orientationof the UTD-1 crystals in which the one-dimensional channels run inparallel along the length of the planks. A cross section of the posthydrothermal PLD film was taken by scratching the film with a diamondscribe.

[0053]FIG. 9 shows a scanning electron micrograph of the cross sectionin which the reorganized film was determined to be about 14 μm thick.The increased reorganized film thickness of the metal beads may beexplained with the increased PLD film associated with the metal beads.Also, as seen in the glass beads, the crystals generated on the metalbeads appeared to be smaller than crystals obtained from flatsubstrates, while being larger than crystals generated from the bulkgel.

[0054] The cross section view in FIG. 9 provided a better view of thedensely packed crystals growing upwards from the substrate surface. Itmay be seen that the plank-like morphologies of the crystals preferredto grow perpendicular to the substrate because of the dense crystalpacking. There were also some broken random crystal observed on the beadsurface, which may be caused by the etching of the film and the crystalsthat were generated by the bulk gel. These scattered crystals wereloosely bound and may be removed by simply blowing air across thesubstrate.

[0055] As a control study, blank beads may also be subjected to ahydrothermal treatment. In this case, UTD-1 crystals are randomlyscattered over the surface of the substrate. Such crystals do notradiate perpendicular from the surface as in the case of the PLDcrystals. Such crystals were, instead, similar to crystals found in abulk gel synthesis. Furthermore, the crystals were loosely bound to thebead's surface, as they tended to detach when blowing air over thesurface or even when washing with water. This unsuccessful attempt toprepare oriented crystals by direct deposition from the gel indicatesthat the uniform pulsed laser deposited film may be essential to theformation of well-adhered, continuous, and oriented coatings, includingUTD-1 coatings.

[0056] In contrast to glass beads which may need a PLD film of about1.75 μm, the stability of metal spheres to high pH may allow fororiented growth from PLD films as thin as about 0.9 μm. The larger metalsphere substrate may generate thicker films than their smaller glassbead counterparts during the crystal reorganization process in the posthydrothermal treatment. The metal beads may have a reorganized crystalgrowth of about 14 μm, in contrast to the approximate 9 μm reorganizedcrystal growth of the smaller glass beads. Increased crystal growth maybe a linear relationship with the size of the substrate. With metalspheres described herein being about 66% larger than the glass beadsdescribed herein, more material may be needed to effectively coat themetal spheres, which may give rise to more nucleation sites.

[0057] Applications for the presently disclosed methods are vast. Usingpulsed laser ablation to coat three dimensional and non-uniform objectsmay be applied commercially in areas such as, but not limited to,separations, catalysis and chemical sensors. The methods may be used tocoat one molecular sieve onto another to enhance catalytic andsize-selective properties. Another application may be utilizingmolecular sieve coated glass beads to pack HPLC columns which, in turn,may enhance selectivity and separation properties of the column.

[0058] The following examples are included to demonstrate specificembodiments of the invention. It should be appreciated by those of skillin the art that the techniques disclosed in the examples which followrepresent techniques discovered by the inventors to function well in thepractice of the invention, and thus may be considered to constitutespecific modes for its practice. However, those of skill in the artshould, in light of the present disclosure, appreciate that many changesmay be made in the specific embodiments which are disclosed and stillobtain a like or similar result without departing from the spirit andscope of the invention.

EXAMPLE 1 Zeolite UTD-1 Coating on Buck Shot Pellets

[0059] Zeolite UTD-1 was synthesized usingbis(pentamethylcyclopentadienly)cobalt (III) hydroxide, Cp*₂CoOH, as thetemplate. The substrates in this Example were spherical, zinc galvanizedcoated steel buck shot pellets measuring about 0.5 mm in diameter andglass beads (Supleco) measuring about 75 μm in diameter.

[0060] A 2.5 cm in diameter pressed pellet of the as-synthesized UTD-1was mounted in a controlled atmosphere chamber at about a 60° C. angleabout 2.5 cm above the substrate holder as shown in FIGS. 1A-1C. Theglass or metal beads were then loaded into a glass dish (about 2.5 cm indiameter and about 1 cm deep) attached to an 8.25×3.2 cm steel plate.The substrate holder sat directly on top of a MOTOROLA® pancake pagervibrator that was controlled by an on/off single speed switch powered bya AA battery. The directional nature of the laser-generated plumeallowed substrates to vibrate in the plume and to become evenly coated.Typical experimental conditions were as follows: laser power was about70 to about 156 mJ/pulse, repetition rate was about 10 Hz, substratetemperature ranged from about 25 to about 60° C., vacuum chamberpressure was about 150 mTorr, and deposition rate was about 70 nm/min atabout 70 mJ/pulse on the non-planar metal bead surface.

[0061] The PLD UTD-1 coated beads were placed in a 23 ml Teflon linedParr reactor containing a UTD-1 synthesis gel having a molar ratio ofSiO₂:Na₂O:CP*₂Co⁺:H₂O of about 1:0.05:0.1:60. The reactor was heated atabout 175° C. for about 72 hours under static conditions. The beads werethen separated from the gel by gravity filtration, washed with deionizedwater, and dried at room temperature. The beads were then calcined inair at about 550° C. for about 6 hours to remove the template.

EXAMPLE 2 Zeolite UTD-1 Coating on Glass Beads and Buck Shot Pellets

[0062] 75 micron glass beads and galvanized coated stainless buck shotpellets have been coated with UTD-1 by pulsed laser ablation (248 μm,KrF*). Typical experimental conditions were as follows: laser power wasabout 70 to about 156 mJ/pulse, repetition rate was about 10 Hz,substrate temperature was about 25 to about 59° C., background pressurewas about 150 mTorr with O₂ deposition rate was about 130 nm/min,deposition time was about 5 minutes to about 13 minutes. The beads orpellets having a UTD-1 coating were placed in a high temperature Teflonliner reactor along with the UTD-1 synthesis gel. A post hydrothermaltreatment was then carried out on these laser deposited substrates forabout 72 hours in an autoclave at about 175 degrees C. resulting in acontinuous highly oriented UTD-1 membrane.

EXAMPLE 3 Zeolite UTD-1 Coating on Glass Beads and Buck Shot Pellets

[0063] Glass beads having a diameter of about 75 microns and galvanizedcoated stainless steel buck shot pellets have been coated with UTD-1 bypulsed laser ablation (248 nm, KrF*). The substrate was placed inside ashallow glass dish, about 2.5 cm in diameter and about 1.21 cm deep, asshown in FIG. 1. The glass dish was mounted on a 8.25″×3.20 cm steelplate, and sat directly on top of a pancake vibrator that was surroundedby a foam ring. The vibrator was controlled by an on/off switch attachedto the steel plate, and was powered by a AA battery. The vibratorapparatus was mounted on a 15.24×7.62 cm stainless steel pipe (notshown) that allowed for the substrate to be placed about 2.5 cm from thetarget. FIG. 1C shows the top view of the vibrator apparatus. Typicalexperimental conditions were as follows: laser power was about 70 toabout 156 mJ/pulse, repetition rate was about 10 Hz, substratetemperature was about 25 to about 59° C., background pressure was about150 mTorr with O₂ and deposition rate was about 130 nm/min. With thevibrator turned on, the pellets vibrated in the plume, allowing theUTD-1 to be deposited uniformly onto the substrates.

[0064] A post hydrothermal treatment was then carried out on these laserdeposited films by placing the pellets in a gel having a molar patio ofSiO₂:Na₂O:CP*₂Co+:H₂O of 0.05:0.1:60 for about 72 hours in an autoclaveat about 175° C. resulting in a continuous highly oriented UTD-1membrane.

EXAMPLE 4 CoAPO-5 Crystals

[0065] CoAPO-5 crystals were coated onto MAPO-39 crystals by pulsedlaser ablation (248 nm, KrF*). The experimental conditions were asfollows: laser power was about 71.2 mJ/pulse, repetition rate was about10 Hz, substrate temperature was about 25° C., background pressure wasabout 150 mTorr with O₂ deposition rate was about 130 nm/min, depositiontime was about 7 minutes and 30 seconds. A coating of CoAPO-5 wasobtained on the MAPO 39 crystals.

EXAMPLE 5 FeAPO-5 Crystals

[0066] FeAPO-5 crystals were coated on MAPO-39 crystals by pulsed laserablation (248 mn, KrF*). The experimental conditions were as follows:laser power was about 71.2 mJ/pulse, repetition rate was about 10 Hz,substrate temperature was about 25° C., background pressure was about150 mTorr with O₂ deposition rate was about 130 nm/min, and depositiontime was about 7 minutes and 30 seconds. A coating of FeAPO-was alsoachieved on MAPO-39 crystals.

[0067] While the invention may be adaptable to various modifications andalternative forms, specific embodiments have been shown by way ofexample and described herein. However, it should be understood that theinvention is not intended to be limited to the particular formsdisclosed. Rather, the invention is to cover all modifications,equivalents, and alternatives falling within the spirit and scope of theinvention as defined by the appended claims. Moreover, the differentaspects of the disclosed compositions and methods may be utilized invarious combinations and/or independently. Thus the invention is notlimited to only those combinations shown herein, but rather may includeother combinations.

REFERENCES

[0068] The following references, to the extent that they provideexemplary procedural or other details supplementary to those set forthherein, are specifically incorporated herein by reference.

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What is claimed is:
 1. A method of coating a substrate, comprising:providing a target; ablating material from said target to create aplume; manipulating the substrate in said plume to coat said substratewith a film; and heating said film in a synthesis gel of said target. 2.The method of claim 1 , wherein heating said film forms an orientedfilm.
 3. The method of claim 2 , wherein said oriented film comprisescrystals normal to the surface of said substrate.
 4. The method of claim1 , wherein said target comprises a zeolite.
 5. The method of claim 4 ,wherein said zeolite comprises at least one of UTD-1, ZSM-5, Beta,Mordenite, NaX, NaA, SSZ-33, SSZ-31, SSZ-42, MCM-22, or a mixturethereof.
 6. The method of claim 1 , wherein said target comprises aphosphate.
 7. The method of claim 6 , wherein said phosphate comprisesan aluminum phosphate.
 8. The method of claim 7 , wherein said aluminumphosphate comprises at least one of VPI-5, AlPO₄-5, AlPO₄-8, or amixture thereof.
 9. The method of claim 6 , wherein said phosphatecomprises a silicon aluminum phosphate.
 10. The method of claim 9 ,wherein said silicon aluminum phosphate comprises at least one ofSAPO-5, SAPO-37, SAPO-42, or a mixture thereof.
 11. The method of claim6 , wherein said phosphate comprises a metal aluminum phosphate.
 12. Themethod of claim 12 , wherein said metal aluminum phosphate comprises atleast one of MAPO-39, MAPO-5, MAPO-11, UCSB-6, UCSB-7, or a mixturethereof.
 13. The method of claim 1 , wherein said target comprises amesoporous molecular sieve.
 14. The method of claim 13 , wherein saidmesoporous molecular sieve comprises at least one of MCM-41, MCM-48,SBA-15, SBA-16, Nb-TMS-1, Ti-TMS-1, Ta-TMS-1, or a mixture thereof. 15.The method of claim 1 , wherein said ablating comprises subjecting saidtarget to pulsed radiation from an excimer laser.
 16. The method ofclaim 15 , wherein said laser comprises a KrF* laser operating betweenabout 70 and about 200 mJ/pulse with a repetition rate between about 1and about 50 Hz.
 17. The method of claim 1 , wherein manipulatingcomprises moving said plume relative to said substrate.
 18. The methodof claim 1 , wherein said manipulating comprises vibrating saidsubstrate.
 19. The method of claim 1 , wherein said heating comprisesheating between about 1 hour and about 200 hours.
 20. The method ofclaim 1 , further comprising adjusting a background pressure of saidsubstrate to between about 150 mTorr and about 350 mTorr.
 21. The methodof claim 20 , wherein said background pressure comprises a backgroundpressure of O₂.
 22. The method of claim 1 , wherein said substratecomprises a zeolite crystal, glass, metal, metal oxide, or plastic. 23.The method of claim 1 , wherein said substrate comprises a poroussubstrate.
 24. The method of claim 1 , wherein a largest dimension ofsaid substrate is between about 10 nm and about 10 mm.
 25. The method ofclaim 1 , wherein said substrate is spherical.
 26. The method of claim 1, further comprising washing or calcining said oriented film.
 27. Acoated substrate made by the method of claim 1 .
 28. A method of coatinga substrate with an oriented film, comprising: providing a targetcomprising Cp*₂Co⁺ or Cp₂Fe; laser ablating material from said target tocreate a plume; vibrating the substrate in said plume to coat a film onsaid substrate; and heating said film in a synthesis gel of said targetto form the oriented film.
 29. The method of claim 28 , wherein saidlaser ablating comprises a first stage and a second stage, said firststage ablating material at a first laser power and said second stageablating material at a second laser power, and wherein said first laserpower differs from said second laser power.
 30. A coated substrate madeby the method of claim 28 .
 31. A method of coating a substrate with anoriented film, comprising: providing a target comprising Cp*₂Co⁺ orCp₂Fe; directing pulsed laser radiation having an energy between about70 mJ/pulse and about 200 mJ/pulse at a repetition rate of between about1 Hz and about 50 Hz to said target to create a plume; heating saidsubstrate; maintaining a pressure between about 150 mTorr and about 350mTorr about said substrate; vibrating said substrate within said plumeto coat a film on said substrate; and heating said film in a synthesisgel of said target to form the oriented film.
 32. The method of claim 31, further comprising washing or calcining said oriented film.
 33. Acoated substrate made by the method of claim 31 .